Antistatic Treatment Agent, and Antistatic Film, Coated Article and Pattern Forming Method Using the Agents

ABSTRACT

The invention provides an antistatic treatment agent having an ability of preventing resist film thinning phenomenon in a chemically amplified resist, an antistatic film, a coated article and a pattern forming method using such antistatic treatment agent, in particular, the invention provides an antistatic treatment agent comprising an aqueous solvent-soluble electroconductive polymer, a diamine (divalent) or polyamine (polyvalent) aliphatic basic compound and an anionic surfactant, an antistatic film, a coated article and a pattern forming method using such antistatic treatment agent. As the aqueous solvent-soluble electroconductive polymer, a π-conjugated electroconductive polymer having a Brönsted acid group is a sulfonic acid group is preferred and it is preferable that the amount of the diamine (divalent) or polyamine (polyvalent) aliphatic basic compound be from 0.1 to 75 mol % based on the total number of moles of the basic compounds.

CROSS-REFERENCE TO RELATED APPLICATIONS

This is an application filed pursuant to 35 U.S.C. Section 111(a) withclaiming the benefit of U.S. provisional application Ser. No. 60/618,569filed Oct. 15, 2004, U.S. provisional application Ser. No. 60/618,571filed Oct. 15, 2004 and U.S. provisional application Ser. No. 60/618,608filed Oct. 15, 2004 under the provision of 35 U.S.C. 111(b), pursuant to35 U.S.C. Section 119(e)(1).

TECHNICAL FIELD

The present invention relates to an antistatic treatment agentcontaining an aqueous solvent-soluble electroconductive polymer and adiamine (divalent) or polyamine (polyvalent) aliphatic basic compound.More specifically, it relates to an antistatic treatment agent, whichhardly forms a mixing layer with a chemically amplified resist employedin semiconductor microprocessing process while maintaining itsantistatic property. Even more specifically, it relates to an antistatictreatment agent which exhibits an excellent wettability with achemically amplified resist. Further, the present invention relates toan antistatic film, a coated article and a pattern forming method usingthe antistatic treatment agent.

BACKGROUND ART

A self-doping type electroconductive polymer is generally soluble inwater and has characteristics of being easily formed in an arbitraryshape, formed in a film or positioned, and is therefore characterizedwith its extremely excellent workability in preparation of a large-areafilm or in an electrical device requiring microfabrication technology.

A charge-up preventing technology utilizing such characteristics in alithographic process employing charged particle beams such as electronbeams of ion beams is disclosed (JP-A No. 4-32848) and is being widelyemployed recently.

A chemically amplified resist, which is an essential material in commontechnology for lithography utilizing light or charged particle beamssuch as electron beams or ion beams, is a resist which is easilyinfluenced by the use environment and is difficult to handle.

In case of coating a surface of the chemically amplified resist with anelectroconductive composition, it is already known that a slight acidcomponent in the coating material can have a significant influence onthe sensitivity of the resist. That is, phenomenons that under a certainhydrogen ion concentration (pH) range, acid generated by exposure isneutralized by the coating material and that acid supplied from thecoating material makes an unexposed part fall in the same state as anexposed part are observed. Such a phenomenon appears as a film thicknessloss in case of a positive type resist, while in case of a negative typeresist, such a phenomenon appears as formation of a hardly soluble layeror an insoluble layer.

For suppressing a pH change in an aqueous solution of an aqueoussolvent-soluble electroconductive polymer, there is disclosed a methodof eliminating oxygen dissolved in the solution (JP-A No. 8-259673) anda method of suppressing a pH decrease by using a buffer solutioncontaining a weak acid and an amine (JP-A No. 11-189746).

Recently there is encountered a problem of resist collapse, caused byreduction in the minimum circuit line width of a semiconductor device,and attempts are being made to select an appropriate aspect ratio inorder to avoid such phenomenon, whereby resist film thickness tends tobecome smaller. A resist patterned through a developing step issubsequently used for a pattern transfer to a substrate by a dry etchingstep, and dry-etching resistance of the resist in this process isbecoming more important, so that requirements for the prevention of afilm thickness loss phenomenon of the resist caused by a charge-uppreventing film and for the maintenance of a resist profile are becomingstricter in recent years.

More specifically, in a process of forming an antistatic treatment filmon a resist surface, in case where a solvent having a high affinity withwater contained in the antistatic treatment agent remains in the resist,the liquid components show mutual penetration. As the aqueoussolvent-soluble electroconductive polymer also migrates with thepenetration of the liquid components, a mixing layer is formed at theinterface between the resist and the antistatic treatment film. When theconcentration of an acid component derived from the aqueoussolvent-soluble electroconductive polymer contained in the mixing layerexceeds the concentration inducing a chemical change of the resist,there is exhibited a film thickness loss phenomenon in case of apositive chemically amplified resist, or formation of a hardly solublelayer or eventually a fogging phenomenon in case of a negativechemically amplified resist. Such an undesired chemical change at theinterface generates a profile called a bowing or a T-top in the resistafter patterning. In the process of transferring such pattern onto asubstrate such as a silicon wafer, the development of such profiledetrimentally affects control of variation in the line width and thedepth and shape of etching, thus constituting a serious problem in finepatterning.

It is known that since chemical amplification resists are mostlyoil-soluble and a coated film thereof is not easily mixed with water, incase of coating a resist surface with an electroconductive composition,a surfactant is added to the electroconductive composition for thepurpose of improving a wettability. However conventional surfactantsthat have been employed often cause an influence on the resist profilesuch as film thickness loss of the resist, while decrease in the amountof the surfactant reduces the wettability, thus affecting the coatingproperty. On the other hand, since the surfactant also has an influenceon the resist, there is disclosed a method of utilizing a water-solublepolymer having a surfactant effect (JP-A No. 2002-226721).

DISCLOSURE OF INVENTION

An object of the present invention is to provide an antistatic treatmentagent having an ability of preventing resist film thinning phenomenon ina chemically amplified resist. Also another object is to provide anantistatic treatment agent having not only an ability of preventingresist film thinning phenomenon but also good coatability. Further,still another object of the present invention is to provide anantistatic film, a coated article and a pattern forming method usingsuch antistatic treatment agent.

The present inventors, as a result of intensive investigations, havefound that an antistatic treatment agent containing an aqueoussolvent-soluble electroconductive polymer and a diamine (divalent) orpolyamine (polyvalent) aliphatic basic compound has an excellent abilityfor preventing film-thinning in a chemically amplified resist and havethus reached the present invention. The present inventors have furtherfound out that if surfactant is added to the agent, the agent canmaintain the ability of preventing film-thinning and exhibits excellentwettability, and have thus completed the present invention.

Thus the present invention relates to a following antistatic treatmentagent, a pattern forming method utilizing an antistatic film using theagent, and various substrate products obtained by utilizing theantistatic film and the pattern forming method.

-   1. An antistatic treatment agent comprising an aqueous    solvent-soluble electroconductive polymer having a Brönsted acid    group and a diamine (divalent) or polyamine (polyvalent) aliphatic    basic compound.-   2. The antistatic treatment agent as described in item 1, further    comprising a volatile basic compound.-   3. The antistatic treatment agent as described in item 1, wherein    the molar ratio of diamine (divalent) or polyamine (polyvalent)    aliphatic basic compound in the total mole number of the basic    compound is within a range of 0.1 to 75 mol. %.-   4. The antistatic treatment agent as described in item 1, wherein at    least one kind of the diamine (divalent) or polyamine (polyvalent)    aliphatic basic compounds has a boiling point of 80° C. or higher.-   5. The antistatic treatment agent as described in item 1, wherein    the diamine (divalent) or polyamine (polyvalent) aliphatic basic    compound consists of one or more kinds selected from a group of a    diaminoalkane, a triaminoalkane, a polyaminoalkane and a    polyalkylimine.-   6. The antistatic treatment agent as described in item 5, wherein    the diamine (divalent) or polyamine (polyvalent) aliphatic basic    compound consists of one or more kinds selected from a group of    ethylenediamine, diaminopropane, diaminobutane, diaminopentane,    diaminohexane, diaminooctane, diaminodecane and polyethyleneimine.-   7. The antistatic treatment agent as described in item 1, wherein    the aqueous solvent-soluble electroconductive polymer is a    π-conjugated electroconductive polymer.-   8. The antistatic treatment agent as described in item 1, wherein    the Brönsted acid group is a sulfonic acid group.-   9. The antistatic treatment agent as described in item 1, wherein    the number of moles of the basic group contained in the diamine    (divalent) or polyamine (polyvalent) aliphatic basic compound is    within a range of 0.05 to 50 mol % based on the number of moles of    the Brönsted acid group contained in the aqueous solvent-soluble    electroconductive polymer.-   10. The antistatic treatment agent as described in item 2, which is    an aqueous solution containing 0.1 to 10 mass % of an aqueous    solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a    diamine (divalent) or polyamine (polyvalent) aliphatic basic    compound and 0.1 to 20 mass % of a volatile basic compound, provided    that the entire amount of the antistatic treatment agent is 100 mass    %.-   11. The antistatic treatment agent as described in item 1, further    comprising a surfactant.-   12. The antistatic treatment agent as described in item 11, wherein    the surfactant is an anionic surfactant, an amphoteric surfactant or    a mixture thereof.-   13. The antistatic treatment agent as described in item 11, wherein    the surfactant is an anionic surfactant.-   14. The antistatic treatment agent as described in item 13, which is    an aqueous solution containing 0.1 to 10 mass % of an aqueous    solvent-soluble electroconductive polymer, 0.1 to 20 mass % of a    diamine (divalent) or polyamine (polyvalent) aliphatic basic    compound, 0.1 to 20 mass % of a volatile basic compound and 0.001 to    1 mass % of an amphoteric surfactant provided that the entire amount    of the antistatic treatment agent is 100 mass %.-   15. The antistatic treatment agent as described in item 1, wherein    the aqueous solvent-soluble electroconductive polymer includes a    chemical structure represented by formula (1):    in the formula, m and n each independently represents 0 or 1; X    represents S, N—R¹ or O; A represents an alkylene group or an    alkenylene group (that may have two or more double bonds) having 1    to 4 carbon atoms and having at least a substituent represented by    -B-SO₃ ⁻M⁺, wherein the alkylene and alkenylene group may be    substituted with a linear or branched, saturated or unsaturated    hydrocarbon group having 1 to 20 carbon atoms, a linear or branched,    saturated or unsaturated alkoxy group having 1 to 20 carbon atoms, a    hydroxyl group, a halogen atom, a nitro group, a cyano group, a    trihalomethyl group, a phenyl group or a substituted phenyl group; B    represents —(CH₂)_(p)—(O)_(q)—(CH₂)_(r)— in which p, q and r    independently represents 0 or an integer of 1 to 3; and M⁺    represents a hydrogen ion, an alkali metal ion, or a quaternary    ammonium ion.-   16. The antistatic treatment agent described in item 1, wherein the    aqueous solvent-soluble electroconductive polymer includes a    chemical structure represented by formula (2):    in the formula, R² to R⁴ each independently represents a hydrogen    atom, a linear or branched, saturated or unsaturated hydrocarbon    group having 1 to 20 carbon atoms, a linear or branched, saturated    or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl    group, a halogen atom, a nitro group, a cyano group, a trihalomethyl    group, a phenyl group, a substituted phenyl group or a -B-SO₃ ⁻M⁺    group; and B and M represent the same meanings as described in item    15.-   17. The antistatic treatment agent as described in item 1, wherein    the aqueous solvent-soluble electroconductive polymer includes a    chemical structure represented by formula (3):    in the formula, R⁵ represents a hydrogen atom, a linear or branched,    saturated or unsaturated hydrocarbon group having 1 to 20 carbon    atoms, a linear or branched, saturated or unsaturated alkoxy group    having 1 to 20 carbon atoms, a hydroxyl group, a halogen atom, a    nitro group, a cyano group, a trihalomethyl group, a phenyl group, a    substituted phenyl group or a -B-SO₃ ⁻M⁺ group; and B, p, q, r and M    represent the same meanings as described in item 10.-   18. The antistatic treatment agent described in item 1, wherein the    aqueous solvent-soluble electroconductive polymer includes a    chemical structure represented by formula (4):    in the formula, R⁶ to R⁸ each independently represents a hydrogen    atom, a linear or branched, saturated or unsaturated hydrocarbon    group having 1 to 20 carbon atoms, a linear or branched, saturated    or unsaturated alkoxy group having 1 to 20 carbon atoms, a hydroxyl    group, a halogen atom, a nitro group, a cyano group, a trihalomethyl    group, a phenyl group, a substituted phenyl group or a SO₃ ⁻M⁺    group; R₉ represents a hydrogen atom or a monovalent group selected    from a group of a linear or branched, saturated or unsaturated    hydrocarbon group having 1 to 20 carbon atoms, a phenyl group and a    substituted phenyl group; and B and M represent the same meanings as    described in item 15.-   19. The antistatic treatment agent as described in item 15 or 16,    wherein the aqueous solvent-soluble electroconductive polymer is a    polymer including 5-sulfonisothianaphthene-1,3-diyl as a chemical    structure.-   20. An antistatic film obtained by using the antistatic treatment    agent as described in any one of the items 1 to 19.-   21. A coated article coated with the antistatic film as described in    item 20.-   22. A coated article described in item 21, wherein the antistatic    film is formed on a photosensitive composition or a charged    particle-sensitive composition coated on a base substrate.-   23. The pattern forming method using the antistatic film as    described in item 20.

Moreover, the invention relates to a following aqueous solution.

-   24. An aqueous solution for antistatic treatment agent comprising a    diamine (divalent) or polyamine (polyvalent) aliphatic basic    compound and an anionic surfactant.-   25. An aqueous solution for antistatic treatment agent comprising a    diamine (divalent) or polyamine (polyvalent) aliphatic basic    compound, a volatile basic compound and an anionic surfactant.-   26. The aqueous solution for antistatic treatment agent as described    in item 24 or 25, wherein the mole fraction of the diamine    (divalent) or polyamine (polyvalent) aliphatic basic compound is    within a range of 0.1 to 75 mol % based on the total number of moles    of the basic compounds.-   27. The aqueous solution for antistatic treatment agent as described    in any one of items 24 to 26, comprising at least one kind of the    diamine (divalent) or polyamine (polyvalent) aliphatic basic    compounds having a boiling point of 80° C. or higher.-   28. The aqueous solution for antistatic treatment agent as described    in any one of items 24 to 27, wherein the diamine (divalent) or    polyamine (polyvalent) aliphatic basic compound consists of one or    more kinds selected from a group of a diaminoalkane, a    triaminoalkane, a polyaminoalkane and a polyalkylimine.-   29. The aqueous solution for antistatic treatment agent as described    in any one of items 24 to 27, wherein the diamine (divalent) or    polyamine (polyvalent) aliphatic basic compound consists of one or    more kinds selected from a group of ethylenediamine, diaminopropane,    diaminobutane, diaminopentane, diaminohexane, diaminooctane,    diaminodecane and polyethyleneimine.

BEST MODE FOR CARRYING OUT THE INVENTION

The antistatic treatment agent contains an aqueous solvent-solubleelectroconductive polymer, and a coating film using the agent and anarticle coated with the agent having electroconductivity are used forantistatic purpose.

The antistatic treatment agent of the invention, if left standing ordried after an application, loses its water content through evaporationor the like, thereby becoming a semi-solid or a solid without fluidity.The agent in such a state with no fluidity is called “antistaticmaterial”, and the antistatic material in a film state is called an“antistatic film”. The present invention will be further clarified inthe following.

The aqueous solvent-soluble electroconductive polymer is generally aπ-conjugated electroconductive polymer having a Brönsted acid group, andis used in a state where a sulfonic acid group or a carboxylic acidgroup derived from the Brönsted acid group is neutralized with a basiccompound. In the present invention, the neutralization is conducted witha mixture consisting of a diamine (divalent) or polyamine (polyvalent)basic compound or another basic compound.

The aqueous solvent-soluble electroconductive polymer, after beingcoated on a resist surface, forms an ionic bond with a basic compoundalong with the evaporation of water, but does not lose mobilitycompletely. Also in case of employing a volatile basic compound, whenthe base substrate is heated together with the resist coated withantistatic film, the ionic bonds formed with the volatile basic compoundare partially decomposed to thereby allow the base component toevaporate, thereby resulting in a drawback that a Brönsted acid thusgenerated affects the resist.

The present inventors have found out that, by neutralizing Brönstedacids in the aqueous solvent-soluble electroconductive polymer with adiamine (divalent) or polyamine (polyvalent) aliphatic basic compound,ionic bonds are formed between the electroconductive polymer and thediamine (divalent) or polyamine (polyvalent) aliphatic basic compound inthe antistatic film formed on the surface of the resist film, therebysuppressing mobility of the electroconductive polymer in the antistaticfilm to thereby prevent mixing at the interface with the chemicallyamplified resist and that it is effective for suppressing film thicknessloss and for maintaining the resist profile.

The diamine (divalent) or polyamine (polyvalent) aliphatic basiccompound to be employed in the invention is not particularly restricted,and specific examples include ethylenediamine, 1,3-propanediamine,1,2-propanediamine, 1,4-butanediamine, 1,5-pentanediamine,1,6-hexanediamine, 1,2-cyclohexanediamine, 1,8-diaminooctane,1,10-decanediamine, 2,3-butanediamine, 1,2-bismethylaminoethane,1,2-bisethylaminoethane, 1,2-bispropylaminoethane,1,2-bisisopropylaminoethane, 2-dimethylaminoethylamine,2-ethylaminoethylamine, 2-isopropylaminoethylamine,2-butylaminoethylamine, 2-propylaminoethylamine,1,2-bisfurfurylaminoethane, 2-furfurylaminoethylamine,1,2,3-triaminopropane, 3,3-diaminodipropylamine and polyethyleneimine,but, in case of electron beam drawing, since the resist is generallysubjected to heating process, a volatile basic compound shows partialdecomposition of the ionic bonds. Therefore, it is preferable that atleast a diamine (divalent) or polyamine (polyvalent) aliphatic basiccompound having a boiling point of 8° C. or higher be contained. Onekind of such diamine (divalent) or polyamine (polyvalent) aliphaticbasic compounds may be employed singly or a mixture of two or more kindsmay be used. Also it may be used in a mixture with other basiccompounds. Preferred examples of other basic compounds include avolatile basic compound. The molar ratio of the diamine (divalent) orpolyamine (polyvalent) aliphatic basic compound is preferably 0.01 to 75mass % based on the entire basic compounds. If the molar ratio is lessthan 0.01 mass %, an effect of the present invention cannot be obtained.If the ratio exceeds 75 mass %, it may cause decrease in theconductivity and insolubilization of the aqueous solvent-solubleelectroconductive polymer, and further, in cases where the agent isapplied in a chemically amplified resist, a quenching of acid generatedby irradiation of charged particle beams.

A volatile basic compound means a compound that is in a gaseous stateunder the normal temperature and the normal pressure, having a boilingpoint of 25° C. or lower, and that is normally handled in a solutionstate. Specific examples include ammonia, methylamine, ethylamine anddimethylamine.

The chemically amplified resist, after generation of an acid catalyst byexposure to light, is heated to accelerate reaction. In a basic compoundhaving a boiling point equal to or lower than the heating temperatureincluding the following basic compounds, like in a volatile basiccompound, ionic bonds between Brönsted acid sites of theelectroconductive polymer, the surfactant and the basic compound arepartially decomposed to allow the base component to evaporate.Therefore, basic compounds having a boiling point equal to or lower thanthe normal heating temperature of the resist, such as isopropylamine,ethylmethylamine, t-butylamine, n-propylamine, isopropylmethylamine,cyclopropylamine, diethylamine, allylamine, isobutylamine orethylpropylamine are included as examples of volatile basic compounds.

The aqueous solvent-soluble electroconductive polymer to be employed inthe present invention basically requires to be a π-conjugatedelectroconductive polymer which has a Brönsted acid group which issoluble in water. The electroconductive polymer is a self-doping typeelectroconductive polymer where the Brönsted acid group is substituteddirectly on the main chain of π-electron conjugation or substituted viaa spacer such as an alkylene side chain or an oxyalkylene side chain,and the chemical structure is not particularly restricted. Specificexamples of the polymer structure include copolymers comprisingrepeating units such as poly(isothianaphthenesulfonic acid),poly(pyrrolealkylsulfonic acid) and poly(anilinesulfonic acid), polymershaving a salt structure thereof and substituted derivatives thereof.

In the aforementioned copolymer, the repeating units having a chemicalstructure containing a sulfonic acid group normally account for 100 to50 mol % based on the total repeating units constituting the polymer,preferably 100 to 80 mol %. The polymer may be a copolymer containingrepeating units of other π-conjugate chemical structures or have acopolymer composition constituted by 2 to 5 kinds of repeating units.

In the invention, “a copolymer containing a repeating unit” is notnecessarily limited to a copolymer containing the repeating unit incontinuous manner but includes a polymer containing the repeating unitin irregular manner or discontinuous manner in the π-conjugate mainchain such as a random copolymer, as long as a desiredelectroconductivity can be exhibited based on the π-conjugate mainchain.

Examples of particularly useful structures in the aqueoussolvent-soluble electroconductive polymer of the invention having theBrönsted acid group include structures represented by formulas (1), (2),(3) and (4). The electroconductive polymer may be a polymer formed by asingle structure of each of these general formulas, or a copolymerincluding such a structure and other structures.

In the formula, m and n each independently represents 0 or 1; Xrepresents S, N—R¹ or O; A represents an alkylene group or an alkenylenegroup (that may have two or more double bonds) having 1 to 4 carbonatoms and having at least a substituent represented by -B-SO₃ ⁻M⁺,wherein the alkylene and alkenylene group may be substituted with alinear or branched, saturated or unsaturated hydrocarbon group having 1to 20 carbon atoms, a linear or branched, saturated or unsaturatedalkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogenatom, a nitro group, a cyano group, a trihalomethyl group, a phenylgroup, or a substituted phenyl group; B represents—(CH₂)_(p)—(O)_(q)—(CH₂)_(r)— in which p, q and r independentlyrepresents 0 or an integer of 1 to 3; and M⁺ represents a hydrogen ion,an alkali metal ion, or a quaternary ammonium ion.

In the formula, R² to R⁴ each independently represents a hydrogen atom,a linear or branched, saturated or unsaturated hydrocarbon group having1 to 20 carbon atoms, a linear or branched, saturated or unsaturatedalkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogenatom, a nitro group, a cyano group, a trihalomethyl group, a phenylgroup, a substituted phenyl group or a -B-SO₃ ⁻M⁺ group. A chain of analkyl group, an alkoxy group or an alkyl ester group of R², R³ or R⁴ mayarbitrarily include a carbonyl bond, an ether bond, an ester bond, asulfonate ester bond, an amide bond, a sulfonamide bond, a sulfide bond,a sulfinyl bond, a sulfonyl bond, or an imino bond. B represents—(CH₂)_(p)—(O)_(q)—(CH₂)_(r)— in which p, q and r independentlyrepresents 0 or an integer of 1 to 3; and M⁺ represents a hydrogen ion,an alkali metal ion, or a quaternary ammonium ion.

In the formula, R⁵ represents a hydrogen atom, a linear or branched,saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms,a linear or branched, saturated or unsaturated alkoxy group having 1 to20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, acyano group, a trihalomethyl group, a phenyl group, a substituted phenylgroup or a -B-SO₃ ⁻M⁺ group. A chain of the alkyl group, the alkoxygroup or the alkyl ester group of R⁵ may arbitrarily include a carbonylbond, an ether bond, an ester bond, a sulfonate ester bond, an amidebond, a sulfonamide bond, a sulfide bond, a sulfinyl bond, a sulfonylbond, or an imino bond. B represents —(CH₂)_(p)—(O)_(q)—(CH₂)_(r)— inwhich p, q and r independently represents 0 or an integer of 1 to 3; andM⁺ represents a hydrogen ion, an alkali metal ion or a quaternaryammonium ion.

In the formula, R⁶ and R⁸ each independently represents a hydrogen atom,a linear or branched, saturated or unsaturated hydrocarbon group having1 to 20 carbon atoms, a linear or branched, saturated or unsaturatedalkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogenatom, a nitro group, a cyano group, a trihalomethyl group, a phenylgroup, a substituted phenyl group or a SO₃ ⁻M⁺ group; and R⁹ representsa hydrogen atom or a monovalent group selected from a group of a linearor branched, saturated or unsaturated hydrocarbon group having 1 to 20carbon atoms, a phenyl group and a substituted phenyl group. A chain ofthe alkyl group, the alkoxy group or the alkyl ester group of R⁶ to R⁸may arbitrarily include a carbonyl bond, an ether bond, an ester bond, asulfonate ester bond, an amide bond, a sulfonamide bond, a sulfide bond,a sulfinyl bond, a sulfonyl bond or an imino bond. B represents—(CH₂)_(p)—(O)_(q)—(CH₂)_(r)— in which p, q and r independentlyrepresents 0 or an integer of 1 to 3; and M⁺ represents a hydrogen ion,an alkali metal ion or a quaternary ammonium ion.

Particularly useful examples for R² to R⁸ in the aforementioned formulaeinclude a hydrogen atom, an alkyl group, an alkoxy group, an alkyl estergroup, a phenyl or substituted phenyl group, and a sulfonic acid group.More specifically, examples of such substituents include, as an alkylgroup, methyl, ethyl, propyl, allyl, isopropyl, butyl, 1-butenyl,pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl,tetradecyl, hexadecyl, ethoxyethyl, methoxyethyl, methoxyethoxyethyl,acetonyl and phenathyl; as an alkoxy group, methoxy, ethoxy, propoxy,isopropoxy, butoxy, pentyloxy, hexyloxy, octyloxy, dodecyloxy,methoxyethoxy and methoxyethoxyethoxy; as an alkyl ester group,alkoxycarbonyl groups such as methoxycarbonyl, ethoxycarbonyl andbutoxycarbonyl, and acyloxy groups such as acetoxy and butyloyloxy; andas a substituted phenyl group, fluorophenyl, chlorophenyl, bromophenyl,methylphenyl and methoxyphenyl. A chain of the alkyl group or the alkoxygroup of R² to R⁸ may arbitrarily include a carbonyl bond, an etherbond, an ester bond, a sulfonate ester bond, an amide bond, asulfonamide bond, a sulfide bond, a sulfinyl bond, a sulfonyl bond, oran imino bond.

Among the aforementioned substituents represented by R² to R⁵ informulas (3) and (4), a hydrogen atom, a linear or branched alkyl oralkoxy group having 1 to 20 carbon atoms are preferred, and a hydrogenatom and a linear or branched alkoxy group having 1 to 20 carbon atomsare particularly preferred.

As a substituent represented by R⁶ to R⁸ in formula (4), a hydrogen atomor a monovalent group selected from a group of a linear or branchedsaturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms,a phenyl group and a substituted phenyl group is preferred.

In formulas (1) to (5), B represents —(CH₂)_(x)—(O)_(y)—(CH₂)_(z)— inwhich x and z independently represents 0 or an integer of 1 to 3, and yrepresents 0 or 1; and in case where all of x, y and z are 0 (x=y=z=0),B does not exist and a sulfur atom otherwise to be bonded to B isdirectly bonded to the bonding site at which B is otherwise to bepresent.

Preferred examples of B include methylene, ethylene, propylene,butylene, pentylene, hexylene, arylene, butadienylene, oxymethylene,oxyethylene, oxypropylene, methyleneoxyethylene and ethyleneoxyethylene.

In —(CH₂)_(x)—(O)_(y)—(CH₂)_(z)— represented by B, there is particularlydesired a case where x and z each independently represents 0 or 1, yrepresents 0 or 1, and z represents 1 in case where y is 1, andparticularly preferable examples of B include a case where B is absentand a sulfur atom is directly bonded (—SO₃ ⁻M⁺), and a case where B ispresent and is methylene (—0CH₂—), dimethylene (—CH₂—CH₂—), oxymethylene(—O—CH₂—), or methyleneoxymethylene (—CH₂—O—CH₂—).

In the formula, M⁺ represents a hydrogen ion, an alkali metal ion or aquaternary ammonium ion, and there may be employed a mixture containingone or more of such cations.

The alkali metal ion can be, for example, Na⁺, Li⁺ or K⁺.

The quaternary ammonium ion is represented by N(R¹⁰)(R¹¹)(R¹²)(R¹³)⁺. Inthe formula, R¹⁰ to R¹³ each independently represents a hydrogen atom, alinear or branched substituted or non-substituted alkyl group having 1to 30 carbon atoms, or a substituted or non-substituted aryl group, orit may also be an alkyl or aryl group including a group containing anelement other than carbon or hydrogen, such as an alkoxy group, ahydroxyl group, an oxyalkylene group, a thioalkylene group, an azogroup, an azobenzene group or a p-diphenyleneoxy group.

As a quaternary ammonium cation represented by N(R¹⁰)(R¹¹)(R¹²)(R¹³)⁺,there is employed a non-substituted, alkyl-substituted oraryl-substituted cation such as NH₄ ⁺, NH(CH₃)₃ ⁺, NH(C₆H₅)₃ ⁺,N(CH₃)₂(CH₂OH)(CH₂-Z)⁺, wherein Z represents an arbitrary substituentwith a chemical formula amount of 600 or less, such as a phenoxy group,a p-diophenyleneoxy group, a p-alkoxydiphenyleneoxy group or ap-alkoxyphenylazophenoxy group. Also for the purpose of converting to aspecified cation, an ordinary ion exchange resin may be used.

The following are examples usable as a constituent unit containing aBrönsted acid and constituting the aqueous solvent-solubleelectroconductive polymer of the present invention. Examples notcorresponding to formulas (1), (2), (3) and (4) includepoly(carbazole-N-alkanesulfonic acid), poly(phenylene-oxyalkanesulfonicacid), poly(phenylenevinylene-alkanesulfonic acid),poly(phenylenevinylene-oxyalkanesulfonic acid),poly(aniline-N-alkanesulfonic acid), poly(thiophenealkylcarboxylicacid), poly(thiopheneoxyalkylcarboxylic acid),poly(polypyrrolealkylcarboxylic acid), poly(pyrroleoxyalkylcarboxylicacid), poly(carbazole-N-alkylcarboxylic acid),poly(phenylene-oxyalkylcarboxylic acid),poly(phenylenevinylene-alkylcarboxylic acid),poly(phenylenevinylene-oxyalkylcarboxylic acid),poly(aniline-N-alkylcarboxylic acid) and a substituted derivativethereof, 6-sulfonaphtho[2,3-c]thiophene-1,3-diyl and a lithium salt, asodium salt, an ammonium salt, a methylammonium salt, an ethylammoniumsalt, a dimethylammonium salt, a diethylammonium salt, atrimethylammonium salt, a triethylammonium salt, a tetramethylammoniumsalt and a tetraethylammonium salt thereof.

Preferred specific examples of the chemical structure represented byformula (1), (2) or (3) include5-(3′-propanesulfo)-4,7-dioxycyclohexa[2,3-c]thiophene-1,3-diyl,5-(2′-ethanesulfo)-4,7-dioxycyclohexa[2,3-c]thiophene-1,3-diyl,5-sulfoisothianaphthene-1,3-diyl, 4-sulfoisothianaphthene-1,3-diyl,4-methyl-5-sulfoisothianaphthene-1,3-diyl,6-methyl-5-sulfoisothianaphthene-1,3-diyl,6-methyl-4-sulfoisothianaphthene-1,3-diyl,5-methyl-4-sulfoisothianaphthene-1,3-diyl,6-ethyl-5-sulfoisothianaphthene-1,3-diyl,6-propyl-5-sulfoisothianaphthene-1,3-diyl,6-butyl-5-sulfoisothianaphthene-1,3-diyl,6-hexyl-5-sulfoisothianaphthene-1,3-diyl,6-decyl-5-sulfoisothianaphthene-1,3-diyl,6-methoxy-5-sulfoisothianaphthene-1,3-diyl,6-ethoxy-5-sulfoisothianaphthene-1,3-diyl,6-chloro-5-sulfoisothianaphthene-1,3-diyl,6-bromo-5-sulfoisothianaphthene-1,3-diyl,6-trifluoromethyl-5-sulfoisothianaphthene-1,3-diyl,5-(sulfomethane)isothianaphthene-1,3-diyl,5-(2′-sulfoethane)isothianaphthene-1,3-diyl,5-(2′-sulfoethoxy)isothianaphthene-1,3-diyl,5-(2′-(2“-sulfoethoxy)methane)isothianaphthene-1,3-diyl,5-(2′-(2“-sulfoethoxy)ethane)isothianaphthene-1,3-diyl and a lithiumsalt, a sodium salt, an ammonium salt, a methylammonium salt, anethylammonium salt, a dimethylammonium salt, a diethylammonium salt, atrimethylammonium salt, a triethylammonium salt, a tetramethylammoniumsalt and a tetraethylammonium salt thereof.

Preferred specific examples of the chemical structure represented byformula (4) include 2-sulfo-1,4-iminophenylene,3-methyl-2-sulfo-1,4-iminophenylene,5-methyl-2-sulfo-1,4-iminophenylene,6-methyl-2-sulfo-1,4-iminophenylene, 5-ethyl-2-sulfo-1,4-iminophenylene,5-hexyl-2-sulfo-1,4-iminophenylene,3-methoxy-2-sulfo-1,4-iminophenylene,5-methoxy-2-sulfo-1,4-iminophenylene,6-methoxy-2-sulfo-1,4-iminophenylene,5-ethoxy-2-sulfo-1,4-iminophenylene, 2-sulfo-N-methyl-1,4-iminophenyleneand 2-sulfo-N-ethyl-1,4-iminophenylene and a lithium salt, a sodiumsalt, an ammonium salt, a methylammonium salt, an ethylammonium salt, adimethylammonium salt, a diethylammonium salt, a trimethylammonium salt,a triethylammonium salt, a tetramethylammonium salt and atetraethylammonium salt thereof.

Since the molecular weight of the self-doping type electroconductivepolymer to be employed in the present invention depends on a chemicalstructure of the repeating unit constituting the polymer, it cannot beflatly defined. However, the polymer may have any molecular weight asfar as the polymer meets the objects of the present invention, andpolymers having the number of repeating unit constituting the main chain(polymerization degree) within a range of 5 to 2,000 and preferably 10to 1,000 can be mentioned.

Particularly preferred examples of the π-conjugated electroconductivepolymer having Brönsted acid group to be employed in the inventioninclude a polymer of 5-sulfoisothanaphthene-1,3-diyl, a random copolymercontaining 80 mol % or more of 5-sulfoisothanaphthene-1,3-diyl,poly(5-sulfoisothanaphthene-1,3-diyl-co-isothanaphthene-1,3-diyl),poly(3-(3-thienyl)ethanesulfonic acid)),poly(3-(3-thienyl)propanesulfonic acid)),poly(2-(3-thienyl)oxyethanesulfonic acid)), a random copolymercontaining 50 mol % or more of 2-sulfo-1,4-iminophenylene, andpoly(2-sulfo-1,4-iminophenylene-co-1,4-iminophenylene), and a lithiumsalt, a sodium salt, an ammonium salt and a triethylammonium saltthereof.

The concentration of the aqueous solvent-soluble electroconductivepolymer differs depending on function desired in the film. However, theconcentration is normally from 0.001 to 30 mass % and preferably 0.01 to10 mass %.

In the antistatic treatment agent of the invention, a solvent misciblewith water and not causing a dedoping of the aqueous solvent-solubleelectroconductive polymer may be employed. Specific examples includeethers such as 1,4-dioxane and tetrahydrofuran, carbonates such asdimethyl carbonate, diethyl carbonate, ethylene carbonate and propylenecarbonate, nitriles such as acetonitrile and benzonitrile, alcohols suchas methanol, ethanol, propanol, and isopropanol, non-protonic polarsolvents such as N,N-dimethylformamide, dimethylsulfoxide andN-methyl-2-pyrrolidone, mineral acids such as sulfuric acid and organicacids such as acetic acid. These may be employed as a mixed solvent oftwo or more kinds.

In the antistatic treatment agent of the present invention, anappropriate amount of surfactant may be added for the purpose ofimproving wettability and coatability. In particular, it is preferableto use a surfactant in a case where the antistatic treatment agent isapplied onto a coating film of a resist having low compatibility withwater.

The surfactant employed in the present invention is not particularlyrestricted and any one of anionic, cationic amphoteric and nonionicsurfactants may be used. Preferred among them are anionic surfactant andamphoteric surfactant.

It is known that, in a case where anionic surfactant or amphotericsurfactant is used, if the surfactant contains a Brönsted acid in itsmolecule, it affects a chemically amplified resist.

In the present invention, Brönsted acids present in anionic surfactantand/or amphoteric surfactant, together with Brönsted acids present inthe aqueous solvent-soluble electroconductive polymer, are neutralizedby a diamine (divalent) or polyamine (polyvalent) aliphatic basiccompound, and thereby crosslinking-like ionic bonds are formed betweenarbitrary Brönsted acid sites of the electroconductive polymer and theanionic surfactant and the basic compound. As a result, the mobility ofthe electroconductive polymer and the surfactant can be suppressed tothereby exhibit an effect of preventing film thinning and also toexhibit an unprecededly excellent wettability.

Specific examples of the anionic surfactant employed in the presentinvention include an alkyl ethersulfonic acid, a linearalkylbenzenesulfonic acid, an α-olefinsulfonic acid, an alkane sulonate,a dialkylsulfosuccinic acid, a naphthalenesulfonic acid-formaldehydecondensate, an ester of alkylsulfuric acid, an ester of polyoxyethylenealkyl ether sulfuric acid, an ester of polyoxyethylene alkylphenyl ethersulfuric acid, a higher alcohol phosphate ester, a higheralcohol-ethylene oxide adduct phosphate ester, and anacyl-N-methyltaurin.

Specific examples of the amphoteric surfactant employed in the presentinvention include quaternary ammonium type surfactants such asmonoalkylammonium, dialkylammonim and ethoxylated ammonium, alkylamines, and guanizine group-containing compounds such as lauroylamideguanidine, and also salts thereof may be used.

One of these anionic or amphoteric surfactants can be employed singly ora mixture of two or more kinds may be employed, and also these may beused in combination with a compound having a surfactant effect such as anonionic or cationic surfactant or a water-soluble polymer.

The amount of the anionic surfactant to be added to the antistatictreatment agent of the present invention is preferably from 0.001 to 1mass %, based on the entire antistatic treatment agent as 100 mass %. Ifthe blending amount is 0.001 mass % or more, the effect of the inventioncan be obtained. If the blending amount is 1% or less, the resistprofile such as film thickness is not affected. The same is true in acase of using an amphoteric surfactant and the same effect can beobtained.

The antistatic treatment agent of the present invention may be used fora non-chemically amplified resist or for a chemically amplified resist.

For a non-chemically amplified resist, the antistatic treatment agent ofthe present invention is effective as an antistatic treatment agent withan excellent coating property. A resin in the non-chemically amplifiedresist is not particularly restricted. Examples thereof include phenolicresins such as novolac resin, poly(methyl methacrylate) resin, acrylicresins such as polyacrylate resin, and a copolymer of α-methylstyreneand α-chloroacrylic acid, however, are not restricted thereto.

For a chemically amplified resist, the present invention preventsformation of a mixing layer at a contact surface between the antistaticfilm of the invention and the chemically amplified resist, and exhibitsan effect of suppressing film thinning in case of a positive typeresist, and exhibits an effect of preventing fogging in case of anegative type resist, and. Examples of components in a composition of achemically amplified resist include a photosensitive resin based onphenolic resin, acrylic resin or azide compound, or a charged particlebeam-sensitive resin based on polymethacrylate resin, polyvinylphenol,polyhydroxystyrene or copolymer of α-methylstyrene and α-chloroacrylicacid, and solvents. Also, as additives, examples include aphotosensitizer, azide compound, crosslinking agent, dissolutioninhibitor and acid generator. Compounds where these additives areintroduced in the main chain or side chain of the polymer may beemployed, however the components are not limited thereto. Specifically,the compound described as an electron-beam resist composition in JP-A2001-281864.

The antistatic treatment agent of the present invention can be regulatedto an arbitrary pH value from acidic to alkaline state, by varying anaddition amount of an amine used for neutralizing the Brönsted acid ofthe aqueous solvent-soluble electroconductive polymer and the anionicsurfactant contained in the solution.

In the present invention, the number of moles of the basic groupcontained in the diamine (divalent) or polyamine (polyvalent) aliphaticbasic compound preferably is from 0.05 to 50 mol % by molar ratio, basedon the number of moles of the Brönsted acid group of the aqueoussolvent-soluble electroconductive polymer. If the number of moles isless than 0.05, an effect of the present invention cannot be obtained.If it exceeds 50 mol %, it may cause reduction in the conductivity andinsolubilization of the aqueous solvent-soluble electroconductivepolymer.

As examples of method of forming an antistatic film on the resistsurface with the antistatic treatment agent, a spin coating isprincipally employed, however various methods can be employed accordingto the purpose of use, such as a dipping (immersion), spraying onto anarticle, ink jet method, screen printing and bar coating method. For thepurpose of coating the antistatic treatment agent of the invention on aresist surface with uniform thickness, spin coating is particularlypreferred.

An article coated with the antistatic film of the present invention is asubstrate on which an antistatic film and a resist are laminated, andexamples of materials for the substrate include silicon wafer, compoundsemiconductor wafers such as gallium arsenide wafer and indium phosphidewafer, quartz and magnetic material, however, are not limited thereto.As such a laminated substrate, substrates in a transitory state inelectron beam lithography including semiconductor manufacturing processor manufacturing process of photomask, reticle or stencil mask areincluded.

Coating the surface with the antistatic film suppresses changes in theresist profile, such as fogging, film thinning, T-top formation orbowing and thereby enables precise pattern formation. Also, the effectof preventing charge-up of the antistatic film can preventmisregistration in lithographic process using charged particle beams,thereby enables pattern formation with higher precision.

The present invention is applicable also to an electronic device. Theelectronic device used here means an electronic device having anantistatic film of the invention between electrodes, and can for examplebe an organic light-emitting device.

Between the electrodes, there may be contained materials other than theantistatic film of the present invention, and there may be provided alaminate structure of an antistatic thin film and thin films of othermaterials.

EXAMPLES

In the following, the present invention will be explained by Examplesand Comparative Examples, but the present invention is not limitedthereto.

The synthesizing method of the aqueous solvent-soluble electroconductivepolymer compound and instruments and methods employed for measuringvarious physical properties in the following examples are as follows.

1) Synthesis of Aqueous Solvent-Soluble Electroconductive PolymerCompound

Poly(5-sulfoisothianaphthene-1,3-diyl) as the aqueous solvent-solubleelectroconductive polymer compound was synthesized by referring to amethod disclosed in JP-A No. 7-48436.

2) pH Measurement

The pH values of aqueous solutions were measured with a hydrogen ionconcentration meter of glass electrode type (pH METER F-13, manufacturedby Horiba Ltd.)

3) Method of Preparation of a Coated Film of the Antistatic TreatmentAgent and Measurement of Surface Resistance

With Spinner 1H-III (manufactured by Kyoei Semiconductor Co. Ltd.), acoated film of antistatic treatment agent was prepared by dropping 2 mlof a composition of an antistatic treatment agent on a Corning #1737glass plate of 60 mm×60 mm×1.1 mm and then spin-coating at 1500 rpm.

The surface resistance of the coated film was measured with a surfaceresistance measuring device MEGARESTER MODEL HT-301 (manufactured bySHISHIDO ELECTROSTATICS, LTD.). The upper limit of measurement for thisdevice was 1×10¹¹Ω/□.

4) Contact Angle

The contact angle was measured with FACE CA-D manufactured by KyowaHyomen Kagaku Co. LTD.

5) Film Thickness Loss of Chemical Amplification Electron Beam Resist(Hereinafter Abbreviated as “Resist”)

Film thickness loss amount of a resist was evaluated in the followingprocedure.

(1) Resist film formation: On a square silicon wafer of 40 mm×40 mm, achemically amplified resist FEP171, manufactured by Fujifilm Arch Co.Ltd., was spin-coated for 60 seconds at 800 rpm, and then a solvent waseliminated by prebaking at 120° C. for 90 seconds.

(2) Measurement of Resist Film Thickness

Resist formed on the substrate was partially peeled off from a part ofthe substrate surface, and then with the surface part as referenceposition, the initial resist film thickness A (nm) was measured by usinga stylus-type surface profiler (Dektak-3030, manufactured by ULVACCorp.).

(3) Formation of Antistatic Film

On the surface coated with resist, 5 ml of an electroconductivecomposition was dropped so as to cover the entire surface of thesubstrate, and was spin-coated with a spin coater at 800 rpm for 60seconds to obtain an antistatic film of a thickness of 0.02 μm.

(4) Baking Process

The substrate having the antistatic film and the resist laminatedthereon was heated, in an air atmosphere, for 90 seconds on a hot platein a reflow oven (manufactured by Sikama International Inc.) byregulating the plate surface temperature at 120° C. under actualmeasurement with a surface temperature meter. Then the substrate of thisstate was let to stand for 30 minutes in the air at the normaltemperature.

(5) Development

2 ml of a developing solution of 2.38 mass % aqueous solution oftetramethyl ammonium hydroxide (TMAH) was dropped on the surface of theantistatic film. After standing for 60 seconds, the developing solutionwas shaken off at 800 rpm, and the film was dried by continuing therotation for 60 seconds.

(6) Postbaking Process

The substrate was let to stand for 10 minutes in an oven heated inadvance to 90° C., for drying.

(7) Resist film thickness B (nm) after development was measured with astylus-type surface profiler, with respect to the part from which theresist had been peeled off in (2) above.

(8) Resist film thickness loss C (C=A−B) was calculated by subtracting Bfrom A.

6) Reference Film Thickness Loss

A resist has a film thickness loss (hereinafter called reference filmthickness loss) D (nm) inherent to each resist, depending on a storageperiod of the coated film, after the preparation of the resist coatedfilm. Such film thickness loss D, which is not attributable to theantistatic film, was measured in advance by the following method.

(1) Resist Film Formation

On a square silicon wafer of 40 mm×40 mm, a chemically amplified resistFEP171, manufactured by Fujifilm Arch Co., Ltd, was spin-coated for 60seconds at 800 rpm, and then a solvent was eliminated by prebaking at120° C.

(2) Measurement of Resist Film Thickness

Resist formed on the substrate was partially peeled off from a part ofthe substrate surface, and then with the surface part as referenceposition, the initial resist film thickness E (nm) was measured by usinga stylus-type surface profiler.

(3) Development

2 ml of a developing solution of 2.38 mass % aqueous solution of TMAHwas dropped on the surface of the antistatic film. After standing for 60seconds, the developing solution was shaken off at 800 rpm, and the filmwas dried by continuing the rotation for 60 seconds.

(4) Postbaking Process

The substrate was let to stand for 10 minutes in an oven heated inadvance to 90° C., for drying.

(5) Resist film thickness F (nm) after development was measured with astylus-type surface profiler, with respect to the part from which theresist had been peeled off in (2) above.

(6) Resist film thickness loss D (D=F−E) was calculated by subtracting Efrom F.

It is preferable that the value obtained by subtracting film thicknessloss C (nm) from reference film thickness loss D (nm) be less than 10nm, particularly preferably less than 3 nm.

Example 1

Into 100 ml of a 0.8 mass % aqueous solution ofpoly(5-sulfoisothianaphthene-1,3-diyl), 0.1 mass % ofdodecylbenzenesulfonic acid was added and the pH was regulated to be 4.5by using a mixed solution of basic compounds formed by 1 mol/l each ofammonia water and an aqueous solution of 1,4-diaminobutane with a ratioof 99% 1%, to thereby obtain antistatic treatment agent 1. Theantistatic treatment agent 1 showed, on a glass substrate, a surfaceresistivity of 4.8×10⁶ ohm/sq.

Example 2

Into 100 ml of a 0.8 mass % aqueous solution ofpoly(5-sulfoisothianaphthene-1,3-diyl), 0.1 mass % ofdodecylbenzenesulfonic acid was added and the pH was regulated to be 4.5by using a mixed solution of basic compounds formed by of 1 mol/l eachammonia water and an aqueous solution of 1,4-diaminobutane with a ratioof 90% 10%, to thereby obtain antistatic treatment agent 2. Theantistatic treatment agent 2 showed, on a glass substrate, a surfaceresistivity of 6.4×10⁶ ohm/sq.

Example 3

Into 100 ml of a 0.8 mass % aqueous solution ofpoly(5-sulfoisothianaphthene-1,3-diyl), 0.1 mass % ofdodecylbenzenesulfonic acid was added and the pH was regulated at 4.5 byusing a mixed solution of basic compounds formed by 1 mol/l each ofammonia water and an aqueous solution of 1,6-hexamethylenediamine with aratio of 99% 1%, to thereby obtain antistatic treatment agent 3. Theantistatic treatment agent 3 showed, on a glass substrate, a surfaceresistivity of 3.9×10⁶ ohm/sq.

Example 4

Into 100 ml of a 0.8 mass % aqueous solution ofpoly(5-sulfoisothianaphthene-1,3-diyl), 0.1 mass % ofdodecylbenzenesulfonic acid was added and the pH was regulated to be 4.5by using a mixed solution of basic compounds formed by 1 mol/l each ofammonia water and an aqueous solution of 16-hexamethylenediamine with aratio of 90%:10%, to thereby.obtain antistatic treatment agent 4. Theantistatic treatment agent 4 showed, on a glass substrate, a surfaceresistivity of 5.1×10⁶ ohm/sq.

Comparative Example 1

Into 100 ml of a 0.8 mass % aqueous solution ofpoly(5-sulfoisothianaphthene-1,3-diyl), 0.1 mass % ofdodecylbenzenesulfonic acid was added and the pH was regulated to be 4.5by using a 1 mol/l aqueous solution of ammonia, to thereby obtainantistatic treatment agent 5. The antistatic treatment agent 5 showed,on a glass substrate, a surface resistivity of 3.3×10⁶ ohm/sq.

Comparative Example 2

Into 100 ml of a 0.8 mass % aqueous solution ofpoly(5-sulfoisothianaphthene-1,3-diyl), 0.1 mass % ofdodecylbenzenesulfonic acid was added and the pH was regulated to be 4.5by using a mixed solution of basic compounds formed by 1 mol/l each ofammonia water and an aqueous solution of ethanolamine with a ratio of50%:50%, to thereby obtain antistatic treatment agent 6. The antistatictreatment agent 6 showed, on a glass substrate, a surface resistivity of4.3×10⁶ ohm/sq.

Results of measurements of a film thickness loss on the antistatictreatment agents of examples 1 tp 4 and comparative examples 1 and 2 areshown in Table 1. TABLE 1 Composition of neutralizing agent (mol. ratio)film thickness loss (nm) Example 1 NH₃ 99% DAB 1% 1 Example 2 90% 10% 3Example 3 99% HMDA 1% 2 Example 4 90% 10% −1 Comp. Ex. 1 100% — — 7Comp. Ex. 1 50% EA 50% 10* NH₃: ammonia water (manufactured by Kanto Chemical Co., Inc.)DAB: 1,4-diaminobutane (manufactured by Acros Organics)HMDA: hexamethylenediamine (manufactured by Kanto Chemical Co., Inc.)EA: ethanolamine (manufactured by Kanto Chemical Co., Inc.)

As shown in Table 1, it was confirmed that the antistatic treatmentsagents containing the diamine (divalent) or polyamine (polyvalent)aliphatic basic compound (Examples 1 to 4) showed almost no filmthickness loss, but the antistatic treatment agents utilizing otherbasic compounds (Comparative Examples 1 and 2) showed film thicknesslosses.

Examples 5 to 14

Into 100 ml of a 0.8 mass % aqueous solution ofpoly(5-sulfoisothianaphthene-1,3-diyl), 0.1 mass % ofdodecylbenzenesulfonic acid was added and the pH was regulated to be 4.5by using a mixed solution of basic compounds formed by 1 mol/l each ofammonia water and diamine (divalent) or polyamine (polyvalent) basiccompounds with a molar ratio shown in Table 2, to thereby obtainantistatic treatment agents.

Results of measurement of contact angle of the antistatic treatmentagents are shown in Table 2. TABLE 2 neutralizing agent composition(mol. ratio) contact angle (°) Example 3 NH₃ 99% HMDA 1% 29.8 Example 595% 5% 22.5 Example 4 90% 10% 16.3 Example 6 80% 20% 14.8 Example 1 99%DAB 1% 31.4 Example 7 95% 5% 26.5 Example 2 90% 10% 22.0 Example 8 80%20% 17.0 Example 9 95% DAPe 5% 19.7 Example 10 90% 10% 16.0 Example 1195% DADPA 5% 24.1 Example 12 90% 10% 20.1 Example 13 95% DAPr 5% 29.0Example 14 90% 10% 24.9 Comp. Ex. 1 100% — — 33.4 Comp. Ex. 2 50% EA 50%34.6* NH₃: ammonia water (manufactured by Kanto Chemical Co., Inc.)HMDA: hexamethylenediamine (manufactured by Kanto Chemical Co., Inc.)DAB: 1,4-diaminobutane (manufactured by Acros Organics)DAPe: 1,3-diaminopentane (manufactured by Tokyo Kasei Kogyo Co., Ltd.)DADPA: 3,3′-diaminodipropylamine (manufactured by Acros Organics)DAPr: 1,3-diaminopropane (manufactured by Kanto Chemical Co., Inc)EA: ethanolamine (manufactured by Kanto Chemical Co., Inc.)

Examples 15 to 17

To 100 mL of aqueous solution, dodecylbenzenesulfonic acid was added inthe blending amount as described in Table 3. Then by adding thereto amixed solution of the basic compound where 1 mol/L each of ammonia waterand an aqueous solution of 1,4-diaminobutane were mixed with theblending ratio of 80%:20%, a water-soluble composition having a pH valueof 4.5 was obtained. The contact angle of the water-soluble compositionfor each of the Examples is shown in Table 3.

Comparative Examples 3 to 5

To 100 mL of water, dodecylbenzenesulfonic acid was added the blendingamount as described in Table 3. Then, by adding thereto 1 mol/L of anaqueous solution of ammonia, a water-soluble composition having a pHvalue of 4.5 was obtained. The contact angle of the water-solublecomposition in each of the Comparative Examples is shown in Table 3.TABLE 3 Neutralizing agent composition Contact (mol ratio) Additiveangle NH₃ DAB  (ppm) (degree) Example 15  80% 20% 2000 18.1 Example 16 80% 20% 1000 21.1 Example 17  80% 20% 500 22.5 Comparative 100% — 200041.5 Example 3 Comparative 100% — 1000 38.7 Example 4 Comparative 100% —500 38.9 Example 5* NH₃: 1 N-ammonia water (manufactured by kanto Chemical Co., Inc.) DAB:1,4-diaminobutane (manufactured by ACROS ORGANICS)

As seen from the results shown in Table 3, the water-solublecompositions of the present invention (Examples 15 to 17) are excellentin wettability compared with the water-soluble compositions ofComparative Examples (Comparative Examples 3 to 5).

Examples 18 to 24

To 100 mL of aqueous solution, n-dodecylbenzenesulfonic acid(manufactured by kanto Chemical Co., Inc.) was added to be 2000 ppm.Then, by using a mixed solution of a basic compound where the componentswere mixed in 1 mol/L each with the blending ratio as shown in Table 4,a water-soluble composition having a pH value of 4.5 for each ofExamples 18 to 24 was obtained. The contact angle of each of thewater-soluble compositions against a FEP171 resist film is shown inTable 4.

Comparative Examples 6 and 7

To 100 mL of water, n-dodecylbenzenesulfonic acid (manufactured by kantoKAGAKU) was added to be 2000 ppm. Then, a mixed solution of 1 mol/L eachof ammonia water (1N-ammonia water manufactured by kanto Chemical, Inc.)and ethanolamine with the ratio as shown in Table 4 was further addedthereto to obtain a water-soluble composition having a pH value of 4.5for each of Comparative Examples 6 and 7. The contact angle of each ofthe water-soluble compositions of Comparative Examples 6 and 7 against aFEP171 resist film is shown in Table 4. TABLE 4 Contact Neutralizingagent composition Additive angle (mol ratio) (ppm) (degree) Example 15NH₃ 80% DAB 20% 2000 18.1 Example 18 95% 5% 2000 32.4 Example 19 95%DAPr 5% 2000 36.2 Example 20 80% 20% 2000 28.0 Example 21 95% HMDA 5%2000 34.7 Example 22 80% 20% 2000 26.7 Example 23 95% DAPe 5% 2000 34.7Example 24 80% 20% 2000 24.5 Comparative 100% — — 2000 41.5 Example 3Comparative 95% EA 5% 2000 38.0 Example 6 Comparative 80% 20% 2000 38.0Example 7* NH₃: 1 N-ammonia water (manufactured by kanto CHEMICAL, INC.)DAB: 1,4-diaminobutane (manufactured by ACROS ORGANICS)HMDA: hexamethylenediamine (manufactured by kanto CHEMICAL, INC.)EA: ethanolamine (manufactured by kanto CHEMICAL, INC.)

It was confirmed that the contact angle against a FEP171 resist filmdecreased by adding a diamine (divalent) or polyamine (polyvalent)aliphatic basic compound to the anionic surfactant in Examples 18 to 24,unlike in Comparative Examples 6 and 7.

1. An antistatic treatment agent comprising an aqueous solvent-solubleelectroconductive polymer having a Brönsted acid group and a diamine orpolyamine aliphatic basic compound.
 2. The antistatic treatment agent asclaimed in claim 1, further comprising a volatile basic compound.
 3. Theantistatic treatment agent as claimed in claim 1, wherein the molarratio of diamine or polyamine aliphatic basic compound in the total molenumber of the basic compound is within a range of 0.1 to 75 mol. %. 4.The antistatic treatment agent as claimed in claim 1, wherein at leastone kind of the diamine or polyamine aliphatic basic compounds has aboiling point of 80° C. or higher.
 5. The antistatic treatment agent asclaimed in claim 1, wherein the diamine or polyamine aliphatic basiccompound consists of one or more kinds selected from a group of adiaminoalkane, a triaminoalkane, a polyaminoalkane and a polyalkylimine.6. The antistatic treatment agent as claimed in claim 5, wherein thediamine or polyamine aliphatic basic compound consists of one or morekinds selected from a group of ethylenediamine, diaminopropane,diaminobutane, diaminopentane, diaminohexane, diaminooctane,diaminodecane and polyethyleneimine.
 7. The antistatic treatment agentas claimed in claim 1, wherein the aqueous solvent-solubleelectroconductive polymer is a π-conjugated electroconductive polymer.8. The antistatic treatment agent as claimed in claim 1, wherein theBrönsted acid group is a sulfonic acid group.
 9. The antistatictreatment agent as claimed in claim 1, wherein the number of moles ofthe basic group contained in the diamine or polyamine aliphatic basiccompound is within a range of 0.05 to 50 mol % based on the number ofmoles of the Brönsted acid group contained in the aqueoussolvent-soluble electroconductive polymer.
 10. The antistatic treatmentagent as claimed in claim 2, which is an aqueous solution containing 0,1to 10 mass % of an aqueous solvent-soluble electroconductive polymer,0.1 to 20 mass % of a di amine or polyamine aliphatic basic compound and0.1 to 20 mass % of a volatile basic compound, provided that the entireamount of the antistatic treatment agent is 100 mass %.
 11. Theantistatic treatment agent as claimed in claim 1, further comprising asurfactant.
 12. The antistatic treatment agent as claimed in claim 11,wherein the surfactant is an anionic surfactant, an amphotericsurfactant or a mixture thereof.
 13. The antistatic treatment agent asclaimed in claim 11, wherein the surfactant is an anionic surfactant.14. The antistatic treatment agent as claimed in claim 13, which is anaqueous solution containing 0.1 to 10 mass % of an aqueoussolvent-soluble electroconductive polymer, 0.1 to 20 mass % of a diamineor polyamine aliphatic basic compound, 0.1 to 20 mass % of a volatilebasic compound and 0.001 to 1 mass % of an amphoteric surfactantprovided that the entire amount of the antistatic treatment agent is 100mass %.
 15. The antistatic treatment agent as claimed in claim 1,wherein the aqueous solvent-soluble electroconductive polymer includes achemical structure represented by formula (1):

in the formula, m and n each independently represents 0 or 1; Xrepresents S, N—R¹ or O; A represents an alkylene group or an alkenylenegroup (that may have two or more double bonds) having 1 to 4 carbonatoms and having at least a substituent represented by -B-SO₃ ⁻M⁺,wherein the alkylene and alkenylene group may be substituted with alinear or branched, saturated or unsaturated hydrocarbon group having 1to 20 carbon atoms, a linear or branched, saturated or unsaturatedalkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogenatom, a nitro group, a cyano group, a trihalomethyl group, a phenylgroup or a substituted phenyl group; B represents—(CH₂)_(p)—(O)_(q)—(CH₂)_(r)— in which p, q and r independentlyrepresents 0 or an integer of 1 to 3; and M⁺ represents a hydrogen ion,an alkali metal ion, or a quaternary ammonium ion.
 16. The antistatictreatment agent described in claim 1, wherein the aqueoussolvent-soluble electroconductive polymer includes a chemical structurerepresented by formula (2):

in the formula, R² to R⁴ each independently represents a hydrogen atom,a linear or branched, saturated or unsaturated hydrocarbon group having1 to 20 carbon atoms, a linear or branched, saturated or unsaturatedalkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogenatom, a nitro group, a cyano group, a trihalomethyl group, a phenylgroup, a substituted phenyl group or a -B-SO₃ ⁻M⁺ group; and B and M⁺represent the same meanings as described in claim
 15. 17. The antistatictreatment agent as claimed in claim 1, wherein the aqueoussolvent-soluble electroconductive polymer includes a chemical structurerepresented by formula (3):

in the formula, R⁵ represents a hydrogen atom, a linear or branched,saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms,a linear or branched, saturated or unsaturated alkoxy group having 1 to20 carbon atoms, a hydroxyl group, a halogen atom, a nitro group, acyano group, a trihalomethyl group, a phenyl group, a substituted phenylgroup or a -B-SO₃ ⁻M⁺ group, and B and M⁺ represent the same meanings asdescribed in claim
 15. 18. The antistatic treatment agent described inclaim 1, wherein the aqueous solvent-soluble electroconductive polymerincludes a chemical structure represented by formula (4):

in the formula, R⁶ to R⁸ each independently represents a hydrogen atom,a linear or branched, saturated or unsaturated hydrocarbon group having1 to 20 carbon atoms, a linear or branched, saturated or unsaturatedalkoxy group having 1 to 20 carbon atoms, a hydroxyl group, a halogenatom, a nitro group, a cyano group, a trihalomethyl group, a phenylgroup, a substituted phenyl group or a SO₃ ⁻M⁺ group; R⁹ represents ahydrogen atom or a monovalent group selected from a group of a linear orbranched, saturated or unsaturated hydrocarbon group having 1 to 20carbon atoms, a phenyl group and a substituted phenyl group; and B andM⁺ represent the same meanings as described in claim
 15. 19. Theantistatic treatment agent as claimed in claim 15, wherein the aqueoussolvent-soluble electroconductive polymer is a polymer including5-sulfonisothianaphthene-1,3-diyl as a chemical structure.
 20. Anantistatic film obtained by using the antistatic treatment agent asdescribed in claim
 1. 21. A coated article coated with the antistaticfilm as claimed in claim
 20. 22. A coated article described in claim 21,wherein the antistatic film is formed on a photosensitive composition ora charged particle-sensitive composition coated on a base substrate. 23.The pattern forming method using the antistatic film as claimed in claim20.
 24. An aqueous solution for antistatic treatment agent comprising adiamine or polyamine aliphatic basic compound and an anionic surfactant.25. An aqueous solution for antistatic treatment agent comprising adiamine or polyamine aliphatic basic compound, a volatile basic compoundand an anionic surfactant.
 26. The aqueous solution for antistatictreatment agent as claimed in claim 24, wherein the mole fraction of thediamine or polyamine aliphatic basic compound is within a range of 0.1to 75 mol % based on the total number of moles of the basic compounds.27. The aqueous solution for antistatic treatment agent as claimed inclaim 24, comprising at least one kind of the diamine or polyaminealiphatic basic compounds having a boiling point of 80° C. or higher.28. The aqueous solution for antistatic treatment agent as claimed inclaim 24, wherein the diamine or polyamine aliphatic basic compoundconsists of one or more kinds selected from a group of a diaminoalkane,a triaminoalkane, a polyaminoalkane and a polyalkylimine.
 29. Theaqueous solution for antistatic treatment agent as claimed in claim 24,wherein the diamine or polyamine aliphatic basic compound consists ofone or more kinds selected from a group of ethylenediamine,diaminopropane, diaminobutane, diaminopentane, diaminohexane,diaminooctane, diaminodecane and polyethyleneimine.